Method, system and device for reducing microbial concentration and/or biofilm formation and/or reducing mineral and chemical concentrations to purify contaminated surfaces and substances

ABSTRACT

Described herein are various methods, systems, and apparatus for reducing and eliminating, microbes, minerals, chemicals and biofilms from contaminated substances. A combination of oxidizing agents and radiation of certain wavelengths forming a synergistic reaction. The synergistic reaction generates EMODs, which are effective in reducing microbial count, unwanted mineral or chemical concentrations and eliminating or blocking biofilm formation, particularly in anaerobic environments. The synergistic reaction produces long lasting EMODs thereby creating a residual effect. This synergistic reaction has a relationship to EMOD creation and has a detrimental effect on microbial contamination (MC), mineral contamination (MINC), chemical contamination (CC), microbial influenced corrosion (MIC) and biofilm creation. MC, MINC, CC, MIC and biofilm can be eliminated or greatly reduced with the treatment methods in or on equipment including pipelines, storage tanks, supplying systems, cooling systems, and processing equipment.

BACKGROUND

The phenomena of microbiological contamination, mineral contamination, chemical contamination and biofilm formation in crude oil, natural gas, hydrocarbons, water, wastewater, production fluids, soil, air and other contaminated substances and surfaces represent a broad problem. Microbial contamination (MC), mineral contamination (MINC), chemical contamination (CC) and microbial influenced corrosion (MIC) all pose severe operational, environmental, and safety problems to the various industries related to petroleum, natural gas, water, wastewater, production fluids, soil and air or other contaminated substances, particularly with respect to degradation of the substances and corrosive damage of equipment used in the storage, processing, and/or transport of raw materials and/or processed products, including but not limited to hydrocarbon substances such as crude, oil and gas, dairy products, food products, water, wastewater, production fluids, soil, air and other contaminated substances.

First, the degradation of petroleum hydrocarbons, water, wastewater, production fluids, soil, air and other contaminated substances is associated with the negative effect of microorganisms. The microbes use material contained in these substances as a source of “food” and change the properties of these substances, thus reducing its value. For example, the changes in oil density, sulfur content and viscosity cause disruption in oil extraction and processing technology, bring about significant economic losses and cause adverse environmental effects. Industry research indicates that 10%-14% of oil and gas is lost due to microbial contamination.

Also, problems influence the ways petroleum hydrocarbons, water, wastewater, production fluids, soil, air and other contaminated substances are stored, transported and processed. The adverse activity of microorganisms causes corrosion of transmission installations (e.g., pipelines of oil, gas, water and wastewater), producing undesirable substances (e.g., H₂S, polymers, organic acids, etc.) that affect the performance and/or quality of the transported substances. Costs resulting from MC, MINC, CC and MIC and biofilm formation in these industries occur due to repair and replacement of damaged equipment, spoilage, environmental clean-up, and injury-related health care, amount to well over several tens of billions of USDs per year. Unwanted mineral concentrations in hydrocarbons and produced water can be divided into two main areas, Sulfur and Iron. Sulfur content of crude oils is one of the most important properties relating to crude oils. Sulfur content is expressed as weight percent of sulfur in oil and typically varies in the range from 0.1 to 5.0% wt. The standard methods that are used to measure the sulfur content are ASTM D129, D1552, and D2622, depending on the sulfur level. Crude oils with more than 0.5% wt sulfur need to be treated extensively during petroleum refining. Using the sulfur content, crude oils can be classified as sweet (<0.5% wt S) and sour (>0.5% % wt S). The distillation process segregates sulfur species in higher concentrations into the higher-boiling fractions and distillation residual. Removing sulfur from petroleum products is one of the most important processes in a refinery to produce fuels compliant with environmental regulations. The typical concentration of iron (II) produced water that results from the fracking process is in the range of 25 to 55 mg/L

The maximum permissible limit for iron (H) in production water that is to be reused or disposed of is 0.5 mg/L, beyond which causes operational issues including pipeline blocking, plugging of formations, corrosion of the metallic parts, and increased turbidity of effluent stream, leading to higher production costs. Even at low concentrations, iron (II) in drinking water can affect aesthetics and other quality such as bad taste and color, staining, and deposition in the water leading to high turbidity. Reusing or disposing of produced water requires mineral contents to be reduced in most instances.

A variety of strategies have been developed to mitigate the negative effects of MC, MINC, CC, MIC and/or the biofilms that contribute or cause MC, MINC, CC and MIC. Such techniques include the use of corrosion resistant metals, oxidizing agents, temperature control, pH control, radiation, filtration, protective coatings with corrosion inhibitors, chemical controls (e.g., biocides, oxidizers, acids, alkalis), bacteriological controls (e.g., phages, enzymes, parasitic bacteria, antibodies, competitive microflora), pigging (i.e., mechanical delamination of corrosion products), anodic and cathodic protection, and modulation of nutrient levels. Attempts to eliminate microorganisms typically involve using chemicals exhibiting biocidal properties, which besides the physical methods is the most popular and most effective technique of eliminating microbiological contamination, microbiological influenced corrosion and biofilm formation. Attempts to eliminate unwanted mineral concentrations typically involve using chemicals exhibiting biocidal properties, flocculants, and precipitants which besides the physical methods are the most popular and most effective technique of eliminating unwanted mineral concentrations. However, the selection of appropriate flocculants, precipitants, antimicrobial or antifungal agents requires the consideration of factors affecting the efficiency of the process. In fact, each of these existing methods face obstacles, such as, high cost, lack of effectiveness, short life-span, or requirement for repeat applications. For example, regular biocide injections are only effective sometimes and only in particular environments. In addition, biocides often fail due to incompatibility with other commonly used corrosion inhibitors and because of biofilm permeability issues, i.e., the biocides are unable to penetrate or permeate the biofilms due to the properties of the extracellular matrix of the biofilms. In addition, many of the above controls are not practical for implementing in many instances due to the potential effect on the downstream processes.

In industry, undesired minerals and chemicals in solution contribute to economic and environmental loss. In the petroleum industry, water produced with hydrocarbons is commonly contaminated with chemicals and/or minerals. Produced water is disposed of in a variety of ways that include reuse, evaporation and injection in disposal wells. Mineral and chemical contaminants, in many cases, need to be reduced or eliminated prior to disposal methods to prevent adverse effects such as ground water contamination, soil contamination and underground water reservoir contamination. Produced water with unwanted high mineral content can also adversely affect underground oil and gas formations by occluding the producing formations.

In pipelines, pigging and biocides are the most commonly used approaches for controlling biofilms and corrosion. Pigging is required to remove or disrupt the biofilm on the pipe surfaces. Pigging can also remove many of the harmful iron sulfide deposits. While pigging will be substantially effective where thick biofilms are present, thin biofilms and thin iron sulfide deposits are not appreciably affected by the scraping action of pigs. Subsequently, biocides and storage systems. However, biocides are not typically effective in penetrating the biofilms, and therefore, have reduced effectiveness against the underlying bacteria. Combination treatments in conjunction with pigging are more effective than the chemical treatments alone. However, treatments must be made routinely on a fixed schedule or else the bacteria population increases significantly, and control becomes even more difficult.

Thus, there exists a need in the art for an improved approach for inhibiting and reducing microbial concentration, mineral concentration, chemical concentrations, and/or biofilm formation that avoids the above indicated problems associated with existing methods, and in particular, which effectively reduces, mitigates, or otherwise eliminates microbial contamination, mineral contamination, chemical contamination, microbial influenced corrosion and/or associated biofilms in/on equipment used to store, transport and/or process crude, oil, gas, hydrocarbons, water, wastewater, food, dairy products, production fluids, soil, air and other contaminated substances.

SUMMARY

Various methods, systems and devices for reducing microbial concentration, mineral concentrations, and chemical concentrations in crude, oil, gas, hydrocarbons, water, wastewater, frack water, produced water from petroleum industry processes, production fluids, soil, food, produce, animals, air and other contaminated substances or for reducing biofilms formed in the substances, on the surface of the substances, or on the surface of equipment involved in the storage, transport or processing of the substances may be shown and described herein. The methods, systems and devices may find application in the oil and/or natural gas production industries, antimicrobial applications, cooling and processing systems of water, decolonization, Fenton's reagent and hydrogen peroxide applications, filamentous bulking control applications, gas scrubbing applications, sulfide oxidation applications, peracetic acid disinfectant application, fracking water decontamination applications, mineral and chemical reduction applications, precipitation applications, etc. More particularly, the methods, systems and devices may be used for mitigating or eliminating microbial contamination (MC), mineral contamination (MINC), and chemical contamination (CC) in crude, oil, gas, hydrocarbons, water, wastewater, production fluids, soil, food, produce, animals, air and other contaminated substances, microbial influenced corrosion (MIC) on metal surfaces, and/or creation and activity of biofilms in these substances.

Exemplary embodiments relate, in part, to a discovery that oxidizing chemicals, together with radiation of certain wavelengths, form a synergistic reaction generating electrically modified oxygen derivatives (EMODs). These EMODs may consist of Reactive Oxygen Species (ROS) and Reactive Nitrogen Species (RNS). The radiation is dosed to create this synergistic reaction with the oxidizing agent. The Physics' definition of “radiation dose” refers to absorbed radiation, and exposure to the incident radiation. Quite frequently dose is used in the biological literature when referring to exposure. Both dose and exposure are quantities integrated over time, they are not rates. The rate quantity corresponding to exposure is irradiance. All these quantities describe radiation as measured on a plane (or flat surface) and are expressed per unit area. Another name for irradiance is ‘vector irradiance’.

Light fluence rate gives the radiation incident on a sphere of unit cross section and is expressed per unit surface area (of the sphere) and per unit time. The corresponding time integrated quantity is light fluence. Another name for fluence rate is ‘scalar irradiance’. Fluence rate and (vector) irradiance are expressed in the same units, but they are different quantities.

In addition, this newly discovered synergistic reaction produces EMODs that exist for a prolonged period of time and in greater numbers than previously recorded. The reaction generates EMODs. A percentage of these EMODs are available to perform antimicrobial activities. A percentage of these EMODs are available to reduce mineral concentrations. A percentage of these EMODs are available to generate additional EMODs. The reduction of oxygen through the addition of electrons leads to the formation of a number of EMODs including: superoxide; hydrogen peroxide; hydroxyl radical; hydroxyl ion; and nitric oxide. The rate of production of EMODs is dependent on the dose of radiation. The EMOD known as a hydroxyl radical has a very short in vivo half-life of approximately 10⁻⁹ seconds in a biologic system and a high reactivity. In an environmental system where antioxidants don't exist, or they exist in small numbers the hydroxyl radicals can exist for minutes. The EMOD known as the hydroxyl ion is a negatively charged molecule consisting of one oxygen atom bonded to one hydrogen atom. When dissolved in water, the hydroxyl ion is an incredibly strong base. In fact, according to the Arrhenius definition of a base, the presence of a hydroxyl ion is what makes a chemical a base. The hydroxyl ion has been demonstrated to exist for over 1 hour. The EMOD known as singlet oxygen exists where the energy difference of 94.3 kJ/mol between ground state and singlet oxygen corresponds to a forbidden singlet-triplet transition in the near-infrared at ˜1270 nm. As a consequence, singlet oxygen in the gas phase is extremely long lived 72 minutes or longer. Our recently discovered process produces EMODs that exist for seconds, minutes, hours and days longer than previously reported. This discovery allows for an oxidizing agent to be exposed to certain wavelengths of radiation and at a dose that is deemed appropriate creating a synergistic effect which produces EMODs that may be available for later use due to the created EMODs long lasting existence. This long-lasting existence can be referred to as a residual effect. Prior to the disclosure, this synergistic reaction involving oxidizing agents and radiation of certain wavelengths was not known or appreciated as to its connection with EMOD creation or its effects on elimination or mitigation of MC, MINC, CC, MIC or biofilm creation.

The resultant synergistic reaction may significantly reduce microbial concentration, mineral concentrations, chemical concentrations and biofilms on surfaces and in solutions, and, consequently, may be used to reduce, mitigate, or eliminate microbial contamination (MC), mineral contamination (MINC), chemical contaminations (CC) in crude, oil, gas, hydrocarbons, water, wastewater, production fluids, soil, air and other contaminated substances and/or microbial influenced corrosion (MIC) on metal surfaces, in particular, metal surfaces of equipment involved in the storage, transport, and processing of these substances. Experiments have demonstrated that the combined synergistic reaction is over 300 percent more effective in elimination of MC, MINC, CC, MIC and/or biofilm formation than either the oxidizing chemicals or the radiation if acting individually. Additionally, generated EMODs are available for a period of time that has previously not been recorded. Research has shown the previously expected EMOD lifespan can now be greatly extended to seconds, minutes, hours, and days. Two of the toughest challenges facing water treatment today are effective iron and hydrogen sulfide removal. As an example, ferrous iron (Fe+2), often occurs naturally in groundwater sources, and can also be found in industrial process and wastewaters, e.g. oil field produced water, steel mills & coal mines (acid mine drainage).

Oxidizing agents can be used to quickly oxidize soluble ferrous iron to ferric (Fe+3), forming a rapidly settling ferric hydroxide floc. The resulting floc can be removed with filtering or a clarifier. An example of this reaction is shown below: 2Fe+2+H2O2+4OH—→2Fe(OH)3(precip.) Hydroxyl radicals bind to ferrous iron to form ferric iron that will precipitate out of a solution. The rate of precipitation is dependent on a number of factors chief of which is the availability of hydroxyl radicals. The described method of using an oxidizing agent in a synergistic reaction with radiation of certain wavelengths in generating an increased number of hydroxyl radicals that are available for longer periods of time than have previously been reported creates a mineral precipitation rate greater than previously available for a given concentration of the oxidizing agent. This provides a cost savings to industry, lessens negative environmental impacts associated with mineral contamination and also provides health benefits created by the removal of unwanted mineral contaminations.

In one aspect, a method for reducing microbial concentration, mineral contamination, and chemical contamination in crude oil, gas, hydrocarbons, water, wastewater, production fluids, soil, air and other contaminated substances or for reducing biofilms formed in the substances, on the surface of the substances, or on the surface of equipment involved in the storage, transport or processing of the substances may be provided. The method may include introducing an effective amount of a composition having an oxidizing agent compound into the substances to be treated and then exposing the resulted mixture of the substances and the composition to radiation of certain wavelengths. The method may include introducing an effective amount of a composition having an oxidizing agent compound while exposing the oxidizing agent to radiation of certain wavelengths as it is introduced into a target substance. The method may include exposing an effective amount of an oxidizing agent compound to radiation of a certain wavelength before it is introduced to a target. The composition comprising the oxidizing agent compound may function together with the radiation of certain wavelengths to lead to a synergistic reaction creating EMODs that exist for a previously undiscovered, longer period of time and in greater quantities than expected from traditional uses of oxidizing agents thereby reducing or eliminating microbes, minerals, chemicals and the biofilm and/or sludge that is associated with them.

In another aspect, a combination for reducing microbial concentration, mineral concentration, and chemical concentration in crude oil, gas, hydrocarbons, water, wastewater, production fluids, soil, air and other contaminated substances or for reducing biofilms formed in the substances, on the surface of the substances, or on the surface of equipment involved in the storage, transport or processing of the substances may be provided. The combination may include a composition having an oxidizing agent compound and radiation of certain wavelengths. The composition including the oxidizing agent compound may function together with the radiation of certain wavelengths to lead to a synergistic reaction creating EMODs that exist for an extended period of time. Previous reports have explained an expected existence of EMODS in biologic systems in nanoseconds. Our newly discovered technology centered on the synergistic reaction between an oxidizing agent and certain wavelengths of radiation demonstrate an EMOD existence measured in seconds, minutes, hours and days. These long lasting EMODs reduce or eliminate unwanted concentrations of microbes, minerals, chemicals and the biofilm and/or sludge that they produce.

In still another aspect, a device for reducing microbial concentration, mineral concentrations, and chemical concentrations in crude oil, gas, hydrocarbons, water, wastewater, production fluids, soil, air and other contaminated substances or for reducing biofilms formed in the substances, on the surface of the substances, or on the surface of equipment involved in the storage, transport or processing of the substances may be provided. The device may include an oxidizing agent introducing component and a radiation emitting component. The oxidizing agent introducing component may be adapted to introduce a composition of an oxidizing agent compound to the hydrocarbon, produced water, frack water, ground water, gas or other targets to be treated. The oxidizing agent introducing component of the device may be, for example, a titration system. The radiation emitting component may be adapted to emit or create radiation of certain wavelengths. The radiation may be applied to the oxidizing agent before, during or after the oxidizing agent is applied to a target. The composition comprising the oxidizing agent compound may function together with the radiation of certain wavelengths to lead to a synergistic reaction creating EMODs that exist for seconds, minutes, hours or days, thereby reducing or eliminating unwanted microbes, minerals, chemicals and the contaminants, biofilms and/or sludge that they produce.

In certain embodiments, the radiation of certain wavelengths may be radiation of a wavelength between 200 nanometers and 700 nanometers, such as from 300 nanometers to 600 nanometers, or from 400 nanometers to 500 nanometers.

In certain embodiments, the effective amount of the oxidizing agent composition may provide the minimal amount of the oxidizing agent compound which results in a measurable or detectable effect on the unwanted microbial, mineral, and/or chemical concentrations or the biofilm formation.

In certain embodiments, the effective amount of the oxidizing agent composition may provide a concentration of the oxidizing agent compound that is from 0.0001 percent to 100 percent or greater, such as from 0.001 percent to 0.3 percent or from 3 percent to 50 percent or greater than 100 percent. of the volume of the substance to be treated. For example, from Higher levels of contamination will require a higher level of an oxidizing agent component to reduce the contaminant level. In cases of the contamination level is so high that it is necessary to use concentrations of oxidizing agents that are greater than the volume of the substance containing the contaminants. Low levels of microbial contamination, mineral contamination, microbial influenced corrosion, and biofilm contamination may be reduced with oxidizing agent concentrations as low as 1 part per million.

In certain embodiments, the effective amount of the composition comprising the oxidizing agent may be determined on the basis of any one or more of the density, pH, temperature, viscosity and light absorbing quality of the substance to be treated, and the size and shape of the container thereof. For example, oil has a density and viscosity that impede the penetration of an oxidizing agent, whereas clean water would not. Moreover, iron precipitates out of solution better in a basic environment, than an acidic one. Further, increasing the temperature may increase the desired reaction rate.

In certain embodiments, the oxidizing agent compound may be hydrogen peroxide, hypochlorous acid, chlorine, peracetic acid, urea, carbamide peroxide, or benzoyl peroxide or any other suitable oxidizing agent.

In certain embodiments, the formulation of the oxidizing agent composition may be determined on the basis of whether the substance to be treated is under aerobic or anaerobic conditions, pH of the substance, mineral content of the target, chemical content of the target salinity of the substance, consortium or population characteristics of the microorganism present in the substance, the microbial content of the substance and/or the microbial content of the biofilms. For example, the formulation may need to be modified for higher mineral and/or chemical contents, which may impede the penetration of an oxidizing agent, and for an iron content, for example, a formulation with a basic pH is better for removal.

In certain embodiments, the composition comprising the oxidizing agent compound may further include at least one other inhibitor against microbial, mineral or chemical contamination in crude, oil, gas, hydrocarbons, water, wastewater, production fluids, soil, air and other contaminated substances and/or microbial influenced corrosion on a metal surface.

In certain embodiments, the at least one other inhibitor may be a biocide selected from a group of germicides, antibiotics, antibacterials, antivirals, antifungals, antiprotozoals and antiparasites.

In certain embodiments, the wavelength, intensity, duration time and/or location relative to the hydrocarbon to be treated, of the radiation, may be determined on the basis of any one or more of the density and light absorbing quality of the crude, oil, gas, hydrocarbons, water, wastewater, production fluids, soil, air and other contaminated substances, the size and shape of the container thereof, whether the substance to be treated is under aerobic or anaerobic conditions, pH of the substance, mineral content of the target, chemical content of the target, temperature of the target, salinity of the substance, consortium or population characteristics of the microorganism present in the substance, and the microbial content of the biofilms. For example, higher mineral and/or chemical contents may require different radiation treatment than lower contents, as the mineral and/or chemical contents may impede the penetration radiation.

In certain embodiments, a secondary treatment may be carried out for reducing unwanted microbial mineral and chemical concentrations or biofilm formation, which may be selected from the group consisting of pigging, sonication, radiation, filtration, stirring, bacteriological control, chemical control, temperature control, pH adjustment, nutrient adjustment, anodic and cathodic protection, protective coating with corrosion inhibitors, and installation of corrosion resistant metals.

In certain embodiments, the unwanted microbial, mineral or chemical concentration or the biofilms may be associated with fungi.

In certain embodiments, the unwanted microbial, mineral, and chemical concentrations or the biofilms may be associated with aerobic bacteria.

In certain embodiments, the unwanted microbial, mineral or chemical concentrations or the biofilms may be associated with anaerobic bacteria.

In certain embodiments, the anaerobic bacteria may be selected from the group of sulfate-reducing bacteria, iron-oxidizing bacteria, sulfur-oxidizing bacteria, nitrate reducing bacteria, methanogens, and acid producing bacteria. The sulfate-reducing bacteria may be of the genera Desulfovibrio, Desulfotomaculum, Desulfosporomusa, Desulfosporosinus, Desulfobacter, Desulfobacterium, Desulfobacula, Desulfobotulus, Desulfocella, Desulfococcus, Desulfofaba, Desulfofrigus, Desulfonema, Desulfosarcina, Desulfospira, Desulfotalea, Desulfotignum, Desulfobulbus, Desulfocapsa, Desulfofustis, Desulforhopalis, Desulfoarculus, Desulfobacca, Desulfomonile, Desulfotigmum, Desulfohalobium, Desulfomonas, Desulfonatronovibrio, Desulfomicrobium, Desulfonatronum, Desulfacinum, Desulforhabdus, Syntrophobacter, Syntrophothermus, Thermaerobacter, and Thermodesulforhabdus.

In certain embodiments, the susceptible metal surface may be a metal surface of equipment for storing, transporting or processing of oil, gas, water, wastewater, production fluids, soil, air and other contaminated substances. Such equipment may be, for example, metal (e.g., steel) pipelines, storage containers, refinery processing equipment and other processing equipment.

In certain embodiments, the oxidizing agent composition including the oxidizing agent compound may be an aqueous composition.

In certain embodiments, the oxidizing agent composition including the oxidizing agent compound may be a non-aqueous composition.

In certain embodiments, the oxidizing agent composition including the oxidizing agent compound may have an acidic pH, ranging from about 6.0-7.0, to about 5.5-6.5, to about 4.5-5.5, to about 3.5-4.5, to about 2.5-3.5, to about 1.5-2.5, or lower than 1.5.

In other embodiments, the oxidizing agent composition including the oxidizing agent compound may have a basic pH, ranging from about 7.0-7.5, to about 7.5-8.5, to about 8.5-9.5, to about 9.5-10.5, to about 10.5-11.5, to about 11.5-12.5, to about 12.5-13.5 to about 14.

In still other embodiments, the oxidizing agent composition including the oxidizing agent compound may have a neutral pH, ranging from about 6-8, or about 6.5-7.5, or about 6.7-7.3, or about 6.8-7.2, or about 6.9-7.1, or about 7.

In still other embodiments, the pH of the environment of or surrounding the substance to be treated and/or its derivatives to be treated may be adjusted with buffers or other pH-altering agents to adjust the pH to any basic, neutral, or acidic conditions.

In certain embodiments, the effective amount of the oxidizing agent composition may be from 3% to 50% weight of the composition, such as depending on viscosity, temperature, density, pH, etc. comprising the oxidizing agent compound may be deposited in the water that exists where the substance to be treated is collected, stored or transported. Recognizing that the microbes require water to survive and multiply, treating the water with the oxidizing agent that has been exposed to radiation, or is exposed to radiation while it is applied or is exposed to radiation after it is applied to a target may create EMODs that reduce or eliminate the MC, MINC, CC, MIC and/or biofilm.

The exemplary methodologies shown and described herein can provide numerous advantageous over existing mitigation practices, such as, but not limited to:

(a) By generating a greater amount of EMODs utilizing the synergistic reaction between an oxidizing agent and certain wavelengths of radiation, reduced quantities of the oxidizing agent may be needed than used in more traditional methods.

(b) By generating longer lasting EMODs utilizing the synergistic reaction between an oxidizing agent and certain wavelengths of radiation, reduced quantities of the oxidizing agent may be needed than used in more traditional methods.

(c) the oxidizing agent may be a natural product of environmental bacteria, hence minimal environmental impact compared to currently available biocides;

(d) in existing methods, biocides are naturally taken up by bacteria in a biofilm and induce a switch to planktonic growth behavior (i.e., growth away from biofilm environment) and thus, lack biofilm permeability aspects needed to better eliminate MC, MINC, CC and MIC;

(e) this MC, MINC, CC and MIC eliminating or reducing treatment may be compatible with commercial corrosion inhibitors, whereas many current biocides are not;

(f) the synergistic reaction between the oxidizing agent and the radiation which produces EMODs presents no negative environmental impact, which is unique compared with current methods of treating MC, MNC, CC and MIC, and thus this invention results in a more complete elimination or reduction in MC, MINC, CC and MIC than currently available methods; and

(g) the reduction in MC, MINC, CC and MIC by the method disclosed in the invention is significantly greater than that by currently available methods when using similar concentrations of oxidizing agents.

BRIEF DESCRIPTION OF THE DRAWINGS

Advantages of exemplary embodiments of the method, combination and device for reducing unwanted microbial, mineral and chemical concentrations or biofilm formation will be apparent from the following detailed description of the exemplary embodiments. The following detailed description should be considered in conjunction with the accompanying figures in which:

FIG. 1 depicts a diagram showing an exemplary embodiment in which a method is applied in a storage tank of crude oil, gas, hydrocarbons, water, wastewater, production fluids, air or other contaminated substance which have less density than water;

FIG. 2 depicts a diagram showing an exemplary embodiment in which a method is applied in a storage tank of crude oil, gas, hydrocarbons, water, wastewater, production fluids, air or other contaminated substance which have greater density than water;

FIG. 3 depicts a diagram showing an exemplary embodiment in which a method is applied in a length of pipeline of crude oil, gas, hydrocarbons, water, wastewater, production fluids, air or other contaminated substance;

FIG. 4 depicts a diagram showing an exemplary embodiment in which a method is applied where crude oil, gas, hydrocarbons, water, wastewater, production fluids, air or another contaminated substance is passed through a series of treatment areas;

FIG. 5 depicts a diagram showing an exemplary embodiment in which the method is applied in the form of a closed loop system for decontaminating a substance to be treated; and

FIG. 6 depicts a diagram showing exemplary an embodiment in which the method is applied in the form of an open loop system for decontaminating a substance to be treated.

FIG. 7 depicts an oxidizing agent titration system where the oxidizing agent is exposed to certain wavelengths of radiation before the oxidizing agent is applied to a target.

DETAILED DESCRIPTION

Aspects of the present invention are disclosed in the following detailed description and related figures directed to specific exemplary embodiments of the invention. Those skilled in the art will recognize that alternative exemplary embodiments may be devised without departing from the spirit or the scope of the claims. Additionally, well-known elements of exemplary embodiments of the invention will not be described in detail or will be omitted so as not to obscure the relevant details of the invention.

As used herein, the word “exemplary” means “serving as an example, instance or illustration.” The embodiments described herein are not limiting, but rather are exemplary only. It should be understood that the described embodiments are not necessarily to be construed as preferred or advantageous over other embodiments. Moreover, the terms “embodiments of the invention”, “embodiments” or “invention” do not require that all embodiments of the invention include the discussed feature, advantage, or mode of operation.

Unless defined otherwise, all technical and scientific terms used herein have the meaning commonly understood by a person skilled in the art to which this disclosure belongs. The following terms may have meanings ascribed to them below, unless specified expressly otherwise. However, it should be understood that other meanings that are known or understood by those having ordinary skills in the art are also possible, and within the scope of the present disclosure.

As used herein, the term “biocide” refers to a chemical substance or microorganism which can deter, render harmless, or exert a controlling effect on any harmful organism by chemical or biological means. Biocides include not just those that are synthetic, but also those that are naturally obtained, e.g., obtained or derived from bacteria and plants. Biocides can include, but are not limited to, germicides, antibiotics, antibacterials, antivirals, antifungals, antiprotozoals and antiparasites. Such compounds that can be used as biocides are well known in the art and may be obtained easily from commercial sources.

As used herein, the terms “microbial contamination” (or “MC”), “mineral contamination” (MINC), “chemical contamination” (CC) and “microbial influenced corrosion” (or “MIC”), or similar terms, are well known terms in the art and shall be understood according to the meaning ascribed in the field. In other words, MC, MINC, CC and MIC mean contamination of crude oil, gas, hydrocarbons, water, wastewater, production fluids, soil, air and other contaminated substances and corrosion to metal surfaces caused directly or indirectly through the effects of bacteria, minerals, chemicals and their byproducts and metabolites, including especially bacteria that grow on the metal surface in a biofilm. MC and MIC can occur in both aerobic and anaerobic conditions and generally are thought to at least require the presence of bacteria in a biofilm. MC is considered “biotic contamination.” MIC is considered “biotic corrosion.” MC, MINC and CC are also associated with sludge formation in crude, oil, gas, hydrocarbons, wastewater, soil, air and other contaminated substances resulting from the growth of microbes therein or in the water associated therewith. MIC, MINC and CC are also associated with surface pitting, which leads to more rapid corrosive failure than uniform corrosion.

As used herein, the term “corrosion associated biofilms” refers to biofilms that have corrosive properties which contribute to microbial influenced corrosion.

As used herein, the term “corrosion” refers to the general deterioration of a material (e.g., metallic material) due to its reaction with the environment.

As used herein, the term “oxidizing agent” refers in chemistry to a substance that has the ability to oxidize other substances—in other words to cause them to lose electrons. Typical oxidizing agents include oxygen, hydrogen peroxide, hypochlorous acid, chlorine, urea and the halogens. In one sense, an oxidizing agent is a chemical species that undergoes a chemical reaction that removes one or more electrons from another atom. In that sense, it is one component in an oxidation-reduction (redox) reaction. In the second sense, an oxidizing agent is a chemical species that transfers electronegative atoms, usually oxygen, to a substrate.

As used herein, “oxidizing agent equivalent” or “oxidizing analog or functionally equivalent compound, molecule or derivative” or similar terms include any known or yet unknown compounds that have a structure that is similar to oxidizing agents to a degree such that they can produce the same or similar biological effects as oxidizing agents.

Common oxidizing agents (O-atom transfer agents) may include, but are not limited to: (1) oxygen (O₂), (2) ozone (O₃), (3) hydrogen peroxide (H₂O₂) and other inorganic peroxides, Fenton's reagent, (4) fluorine (F₂), chlorine (Cl₂) and other halogens, (5) nitric acid (HNO₃) and nitrate compounds, (6) sulfuric acid (H₂SO₄), (7) peroxydisulfuric acid (H₂S₂O₈), (8) peroxymonosulfuric acid (H₂SO₅), (9) chlorite, chlorate, perchlorate, and other analogous halogen compounds, (10) hypochlorite and other hypohalite compounds, including household bleach (NaClO), (11) hexavalent chromium compounds such as chromic and dichromic acids and chromium trioxide, pyridinium chlorochromate (PCC), and chromate/dichromate compounds, (12) permanganate compounds such as potassium permanganate, (13) sodium perborate, (14) nitrous oxide (N₂O), nitrogen dioxide (NO₂), dinitrogen tetroxide (N₂O₄), (15) potassium nitrate (KNO₃), the oxidizer in black powder, (16) sodium bismuthate, (17) peracetic acid and (18) urea.

As used herein, the term “radiation” refers in physics to the emission or transmission of energy in the form of waves or particles through space or through a material medium. This includes, but is not limited to: (1) electromagnetic radiation, such as radio waves, microwaves, ultraviolet light, visible light, x-rays, and gamma (γ) radiation, (2) particle radiation, such as alpha (α) radiation, beta (β) radiation, and neutron radiation (particles of non-zero rest energy), (3) acoustic radiation, such as ultrasound, sound, and seismic waves (dependent on a physical transmission medium), and (4) gravitational radiation, radiation that takes the form of gravitational waves, or ripples in the curvature of spacetime.

The word “radiation” arises from the phenomenon of waves radiating (i.e., traveling outward in all directions) from a source. This aspect leads to a system of measurements and physical units that are applicable to all types of radiation. Because such radiation expands as it passes through space, and as its energy is conserved (in vacuum), the intensity of all types of radiation from a point source follows an inverse-square law in relation to the distance from its source. Like any ideal law, the inverse-square law approximates a measured radiation intensity to the extent that the source approximates a geometric point. Some of the ultraviolet spectrum that begins above energies of 3.1 eV, a wavelength less than 400 nm is non-ionizing, but is still biologically hazardous due to the ability of single photons of this energy to cause electronic excitation in biological molecules, and thus damage them by means of certain reactions. This property gives the ultraviolet spectrum some of the properties of ionizing radiation in biological systems without actual ionization occurring. In contrast, visible light and longer-wavelength electromagnetic radiation, such as infrared, microwaves, and radio waves, consists of photons with too little energy to cause damaging molecular excitation. Light, or visible light, is a very narrow range of electromagnetic radiation of a wavelength that is visible to the human eye, or 380-750 nm which equates to a frequency range of 790 to 400 THz respectively. More broadly, physicists use the term “light” to mean electromagnetic radiation of all wavelengths, whether visible or not.

As used herein, the term “sulfate-reducing bacteria” or “SRB,” which are considered one of the main culprits of biotic contamination and biotic corrosion in anaerobic conditions, are a grouping of bacteria that includes at least 220 species which produce H₂S and use sulfates as the terminal electron acceptor. Most SRB are considered obligate anaerobes, meaning that the cells cannot metabolize and/or replicate in the presence of oxygen, although many species can temporarily tolerate low levels of oxygen. Furthermore, anaerobic conditions capable of supporting SRB growth can be created in overall aerobic environments, due to the micro-niches created within the bacterial biofilm/corrosion product layer. Although SRB are the most studied and well understood of the anaerobic corrosion inducing bacteria, both MC and MIC can occur in anaerobic conditions in the absence of SRB.

As used herein, the term “pigging” refers to a well-known process of intentional mechanical delaminating corrosion products and/or biofilm material from metal surfaces.

As used herein, the singular forms “a”, “an”, and “the” include plural references unless the context clearly dictates otherwise. All numerical values within the detailed descriptions and the claims herein are modified by “about” or “approximately” the indicated value and take into account experimental error and variations that would be expected by a person having ordinary skills in the art.

Reference will now be made in detail to exemplary embodiments of the disclosure. In certain exemplary embodiments, and generally referring to FIGS. 1-3, a system, device and method of reducing microbial, mineral and chemical concentrations in crude oil gas, hydrocarbons, water, wastewater, production fluids, soil, air and other contaminated substance or for reducing biofilms formed in the substance, on the surface of the substance, or on the surface of equipment involved in the storage, transport or processing of the substance may be shown and described. It will be appreciated that this disclosure provides an effective and cost-efficient solution to solve the problem of microbial contamination (MC), mineral contamination (MINC), and/or chemical contamination (CC) in a composition comprising crude oil, gas, hydrocarbons, water, wastewater, production fluids, soil, air and other contaminated substance or their derivatives or a functionally equivalent analog or derivative and water. Also provided may be a solution to solve the problem of microbial influenced corrosion (MIC) on solid surfaces, such as surface of the equipment used in the petroleum and natural gas industries to store, transport, and process raw or refined materials (e.g., crude oil, gas, water, wastewater, production fluids, and other processed substances). Additionally, this disclosure may provide an effective and cost-effective solution for preventing and/or mitigating the formation of harmful biofilms associated with microbial contamination and/or microbial influenced corrosion of metal surfaces of the production, storage, and transport equipment of crude, oil, gas, hydrocarbons, water, wastewater, production fluids, soil, air and other contaminated substance.

While the disclosure will be described in conjunction with the exemplary embodiments, one skilled in the art can understand that it is not intended to limit the disclosure to those embodiments. Any combination, devices or methods provided herein can be combined with one or more of any of the other combination, devices and methods provided herein. To the contrary, this invention is intended to cover alternatives, modifications, and equivalents as may be included within the spirit and scope of the disclosure as defined by the appended claims.

Penetration and Development of Microorganisms

Microorganisms may penetrate into oil fields as a result of drilling, and/or into oil and fuel storage tanks, oil pipelines and transmission facilities, which are the perfect place for colonization by both aerobic and anaerobic microorganisms. The stages during which microorganisms may emerge are commonly: (1) stage of application of drilling fluids, which may be contaminated in this way allochthonous bacteria are introduced to the deposit, (2) stage of supply—borehole watering with highly contaminated water, (3) stage of oil transport—presence of microorganisms in contaminated water in transmission systems, (4) petroleum processing stage, and (5) stage of storage of crude oil and its processing products. It is extremely difficult to prevent microbiological contamination because it is impossible to maintain sterile conditions during the extraction, transport and storage of crude oil. In fact, at each stage of oil processing from its exploitation, transport, processing and ending with the storage, it can be subjected to the action of microorganisms. Similar routes of contamination exist with water, wastewater, production fluids, soil, air and other substances, paper mills and cooling systems.

A necessary condition for the emergence and development of microorganisms is the presence of carbon source in a given environment (e.g., tanks, pipelines, storage, supply systems, etc.). The deterioration of crude, oil, gas, hydrocarbons, water, wastewater, production fluids, soil, air and other products under the influence of microbial activity reduces the economic value of the substance because they are being used as a carbon source in both aerobic and anaerobic conditions.

Another essential and necessary condition for the growth of microorganisms in crude oil, gas, hydrocarbons, water, wastewater, production fluids, soil, air and other contaminated substance or products of its processing is the presence of water, the accumulation of water condensation in pipelines during transmission or in the tanks during storage of the substance. The existence of the possibility of interactions between the carbon source and water adds complexity of the issue of microbial contamination, microbial influenced corrosion and biofilm creation.

Bacteria and fungi are two main groups of microorganisms that contaminate the storage, transport and production process of the substance. Both bacteria and fungi require food and water to thrive. In a storage tank their “food” is, for example, oil or other carbon source. They get water from the water that collects in the storage tank and get food from the carbon-water interface. The resulting microbial slimes (biofilms) are from the unchecked growth of these microorganisms that are always present in air, fuel, and water. Microorganisms will degrade the production, storage and transport systems if left unmitigated.

MC, MINC, CC, MIC and Biofilms

Microbial contamination (MC), Mineral contamination (MINC), Chemical contamination (CC), microbial influenced corrosion (MIC) and/or biofilm formation is frequently observed at the production sites of crude oil, gas, hydrocarbons, water, wastewater, production fluids, soil, air and other contaminated substances and in transport pipelines, and among other types of equipment involved in the production industry of crude oil, gas, hydrocarbons, water, wastewater, production fluids, soil, air, and other contaminated substance.

The mechanisms by which microbial contamination (MC), mineral contamination (MINC), chemical contamination (CC), microbial influenced corrosion (MIC) and/or biofilm creation causes damage are not fully understood despite many decades of research. However, microbial contamination (MC), mineral contamination (MINC), chemical contamination (CC), microbial influenced corrosion (MIC) and/or the biofilms created pose severe operational, environmental, and safety problems to the related industries, particularly with respect to contamination in crude oil, gas, hydrocarbons, water, wastewater, production fluids, soil, air and other contaminated substances and corrosion of equipment used in the storage, processing, and/or transport of the substance. Costs resulting from MC, MINC, CC and MIC in these industries due to repair and replacement of damaged equipment, spoiled products, environmental clean-up, and injury-related health care, amount to well over several tens of billions of USDs per year, posing a major economic problem for the related industries, as well as a huge threat to the environment.

Development and metabolic activity of microflora directly leads to the deterioration of the physico-chemical parameters of crude oil, gas, hydrocarbons, water, wastewater, production fluids, soil, air, and other contaminated substance. A negative phenomenon is the precipitation of biomass (sludge), which are metabolic products of fungi, bacteria, yeast, etc. The biomass, or sludge, forms larger agglomerates. This causes the silting of reservoir rocks, clogging of pipelines, and accumulation of sediments at the bottom of storage and transport tanks. The number of microorganisms (bacteria and fungi) in the aqueous layer contained in petroleum products including crude oil, gas, and hydrocarbons, water, wastewater, production fluids, soil, air and other contaminated substance, determines the amount of contamination.

Also, microbial contamination, mineral contamination, chemical contamination and microbial influenced corrosion leads to additional corrosion, often characterized by or with pitting of metal surfaces caused by sulfate-reducing bacteria, and frequently results in extensive damage to the storage, production, and transportation equipment. Pipe systems, tank bottoms, and other pieces of storage and production equipment can rapidly fail if there are areas where microbial corrosion is occurring. If a failure occurs in a pipeline or storage tank bottom, the released substance can have serious environmental consequences. More crucially, if a failure occurs in a high-pressure liquid or gas line, the consequences may be worker injury or death. Any failure at least involves significant repair or replacement costs.

There are several stages during which microbiological, mineral, and chemical contamination of crude oil, gas, hydrocarbons, water, wastewater, production fluids, soil, air and other contaminated substances and their derivatives may occur. In the initial stages of growth, the organisms present are predominantly aerobic, using the dissolved oxygen in the water for respiration. As this supply of oxygen is depleted, anaerobic bacteria (typically known as sulfate-reducing bacteria) develop. These organisms do not require oxygen for respiration and form corrosive waste products. One waste expelled by the organisms is hydrogen sulfide. Sulfate-reducing bacteria also use the enzyme hydrogenase, which scavenges hydrogen ions from the metallic surfaces beneath biofilms. Hydrogenase activity accelerates galvanic corrosion. Other anaerobic bacteria growing produce weak organic acids. The weak organic acids react readily with chloride, nitrate, nitrite, and sulfate anions to form strong inorganic acids, which attack infrastructure surfaces.

The microorganisms thought to be primarily responsible for corrosion at least in an anaerobic environment within the related industries are sulfate-reducing bacteria. Other culpable bacteria include iron-oxidizing bacteria, sulfur-oxidizing bacteria, nitrate reducing bacteria, methanogens, and acid producing bacteria, among others. These categories of bacteria generally are capable of reducing metal directly, producing metabolic products that are corrosive and/or leading to the formation of biofilms that indirectly alter the local environment to promote corrosion and sludge formation.

Sulfate-reducing bacteria, in particular, are ubiquitous and can grow in almost any environment. They are routinely found in waters associated with production systems of crude, oil, gas, hydrocarbons, water, wastewater, production fluids, soil, air and other contaminated substance and can be found in virtually all industrial aqueous processes, including cooling water systems and petroleum refining. Sulfate-reducing bacteria require an anaerobic (oxygen-free) aqueous solution containing adequate nutrients, an electron donor, and an electron acceptor. A typical electron acceptor is sulfate, which produces hydrogen sulfide upon reduction. Hydrogen sulfide is a highly corrosive gas and reacts with metal surfaces to form insoluble iron sulfide corrosion products. In addition, hydrogen sulfide partitions into the water, oil, and natural gas phases of produced fluids and creates a number of serious problems. For instance, “sour” oil or gas, which contains high levels of hydrogen sulfide, has a lower commercial value than low sulfide oil or gas. Removing biogenic hydrogen sulfide from sour oil and gas increases the cost of these products. It is also an extremely toxic gas and is immediately lethal to humans at even small concentrations. Thus, its presence poses a threat to worker safety.

It is believed that microbial contamination and microbial influenced corrosion are primarily caused by the formation of microbial biofilms in equipment that comes into contact with crude oil, gas, hydrocarbons, water, wastewater, production fluids, soil, air and other contaminated substance and/or the liquid systems involved in its storage, transport and/or processing.

Biofilms and Treatable Surfaces

Microorganisms present in aqueous environments form biofilms on surfaces. Biofilm consists of populations of microorganisms and their hydrated polymeric secretions. Numerous types of organisms may exist in any particular biofilm, ranging from strictly aerobic bacteria at the water interface to anaerobic bacteria such as sulfate-reducing bacteria (SRB) at the oxygen depleted metal surface.

Biofilm formation is thought to follow a multi-series of specific steps that include: (a) an initial bacterial attachment stage that is rapid and reversible; (b) a longer termed attachment stage; (c) a replication phase; (d) a polysaccharide-rich matrix secretion stage; (e) a biofilm maturation stage; and (f) finally, a bacterial dispersal stage. Biofilms can be microns of millimeters to centimeters or more in thickness and can develop over the course of hours, days, or months, depending on many factors that include the consortium of bacteria present and the environment.

Biofilms are highly complex, naturally occurring biotic structures which have a wide range of characteristics. Their exact role in corrosion is still under intense study. However, biofilm-associated corrosion is at least a function of the composition of the underlying bacterial population that forms the biofilm and on the environment. The presence of biofilm can contribute to corrosion in at least three ways: (1) physical deposition, (2) production of corrosive byproducts, and (3) depolarization of the corrosion cell caused by chemical reaction.

Many of the byproducts of microbial metabolism, including organic acids and hydrogen sulfide, are corrosive. These materials can concentrate in the biofilms, causing accelerated metal attack and corrosion. Corrosion tends to be self-limited due to the buildup of corrosion reaction products. However, microbes can absorb some of these materials in their metabolism, thereby removing them from the anodic and cathodic sites. The removal of reaction products, termed depolarization, stimulates further corrosion.

Biofilms are usually found on solid substrates submerged in or exposed to an aqueous solution, although they can form as floating mats on liquid surfaces and also on the surface of debris, particularly in high humidity climates. Given sufficient resources for growth, a biofilm will quickly grow to be macroscopic. Biofilms can contain many different types of microorganism, e.g., bacteria, archaea, protozoa, fungi and algae; each group performs specialized metabolic functions. However, some organisms will form single species films under certain conditions. The social structure (cooperation, competition) within a biofilm highly depends on the different species present.

Biofilms are held together and protected by a matrix of secreted polymeric compounds called EPS. EPS is an abbreviation for either extracellular polymeric substance or exopolysaccharide, although the latter one only refers to the polysaccharide moiety of EPS. In fact, the EPS matrix consists not only of polysaccharides but also of proteins (which may be the major component in environmental and wastewater biofilms) and nucleic acids. A large proportion of the EPS is more or less strongly hydrated; however, hydrophobic EPS also occur; one example is cellulose which is produced by a range of microorganisms. This matrix encases the cells within it and facilitates communication among them through biochemical signals as well as gene exchange. The EPS matrix is an important key to the evolutionary success of biofilms and their resistance to, in this case, biocides and other chemical treatments to remove them. One reason is that it traps extracellular enzymes and keeps them in close proximity to the cells. Thus, the matrix represents an external digestion system and allows for stable synergistic microconsortia of different species. Some biofilms have been found to contain water channels that help distribute nutrients and signaling molecules.

Despite these protective physical and biological properties of biofilms and in particular, the EPS which presents a significant permeability barrier to antibacterial agents, oxidizing agents (and oxidizing agent analogs) has been shown by the inventor to be effective in mitigating the formation of biofilms on metal surfaces, in particular, under anaerobic conditions.

Biofilms that form in the substances or on the surfaces of such metal components are thought to be the primary causative agent triggering corrosion. Many biofilm-forming environmental bacteria, particularly those in anaerobic environments, produce harmful gases (e.g., hydrogen sulfide), acids (e.g., sulfuric acid), and other agents which are highly corrosive and also which pose health and safety concerns to those workers in the industry. Currently, mitigation techniques to reduce microbial induced corrosion are available but are not often effective enough and/or are not practical in the industry due to high cost, limited efficacy and other reasons. For example, the use of current biocides is common, but their effectiveness is limited due to inability to permeate the corrosive biofilms.

EMODs and Synergistic Chemical Reaction

As shown in exemplary embodiments herein, oxidizing agent compositions and compounds that are functionally equivalent to oxidizing agents, when combined with radiation of certain wavelengths may significantly reduce unwanted microbial, mineral and chemical concentrations and/or formation of biofilms. Consequently, such compositions and compounds may be used to reduce, mitigate, or eliminate unwanted microbial, mineral and chemical contaminations in crude oil, gas, hydrocarbons, water, wastewater, production fluids, soil, air and other contaminated substances and/or microbial influenced corrosion on metal surfaces, and in particular, metal surfaces on equipment involved in the storage, transport, and processing of the crude, oil, gas, hydrocarbons, water, wastewater, production fluids, soil, food, air and other contaminated substances.

The interest in environmentally friendly, non-toxic and degradable yet potent biocides has never been higher. Oxidizing agents have been extensively used as such biocides, particularly in applications where its decomposition into non-toxic byproducts is important. The majority of studies investigating the microbe toxic mechanism of oxidizing agents consider them as a source of oxidative stress in the cell to model chronic oxidative damage to cells. When used to treat microbes, oxidizing agents exhibit non-resistant characteristics, and thus have broad-spectrum antibacterial and antimicrobial effects. Oxidizing agents, notably hydrogen peroxide (H₂O₂), are increasingly used in a number of medical, food and industrial applications but also in environmental applications. Oxidizing agents and their associated EMODs cause many minerals and chemicals to precipitate out of solution. This creates the ability to filter out many of the unwanted minerals and chemicals. This invention increases both the quantity and the functional duration of EMODs created by the synergistic reaction of an oxidizing agent and certain wavelengths of radiation.

Electronically modified oxygen derivatives (EMODs) are chemically reactive chemical species containing oxygen. Examples of EMODs include peroxides, superoxide, hydroxyl radical, and singlet oxygen. EMODs may serve as an antimicrobial defense. EMODs may precipitate minerals and chemicals out of solutions. Individuals with chronic granulomatous disease who have deficiencies in generating EMODs, are highly susceptible to infection by a broad range of microbes including Salmonella enterica, Staphylococcus aureus, Serratia marcescens, and Aspergillus spp. A role for EMODs in antiviral defense mechanisms also can be demonstrated via Rig-like helicase-1 and mitochondrial antiviral signaling protein. Increased levels of EMODs potentiate signaling through this mitochondria-associated antiviral receptor to activate interferon regulatory factor (IRF)-3, IRF-7, and nuclear factor kappa B (NF-κB), resulting in an antiviral state.

EMODs may be generated through a synergistic chemical reaction of oxidizing agents and ionizing/nonionizing radiation. In a chemical compound, these generated EMODs are in addition to the commonly occurring EMODs that are utilized currently in industry and science. During the process that the radiation and the oxidizing agents interact, damaging intermediates may be created. Oxidizing chemicals may be used as the precursors to EMODs, while the radiation may function as an exogenous source. This type of synergistic reaction may lead to a situation where the resulted antimicrobial effect is much greater than the sum of the effect caused by individual components of the reaction. In addition, EMODs created by this synergistic reaction exist much longer than the expected life of nanoseconds that current literature describes. EMODs generated by this synergistic reaction exist for lengths of time previously undiscovered. This previously undiscovered length of time can be seconds, minutes, hours and days. For example, EMODs can last 1 minute, 5 minutes, 10 minutes, 30 minutes, 1 hour, 12 hours, 24 hours, 2 days, 5 days or 7 days. The EMODs presence is demonstrated by a continued antimicrobial effect, or reduction in microbial content during a given time period, as compared to a control. Due to the higher concentration of EMODs, this new discovery allows for greater functionality of a specific concentration of an oxidizing agent then is currently available from that concentration. For example, 0.3% of hydrogen peroxide that is exposed to radiation as described, may produce similar antimicrobial effects as 3% hydrogen over a 12 hour period. Additionally, this discovery allows for the synergistic reaction between an oxidizing agent and certain wavelengths of radiation to take place minutes, hours, or days before this compound that exhibits increased functionality is applied to a target. By utilizing the higher concentration of EMODs, this results in economic savings and a more environmentally friendly method of eliminating unwanted MC, MIC, MINC, and CC.

In the synergistic reaction process, water loses an electron and becomes highly reactive. Then through a three-step chain reaction, water is sequentially converted to hydroxyl radical (•OH), hydrogen peroxide (H₂O₂), superoxide radical (•O⁻²) and ultimately oxygen (O₂). The hydroxyl radical is extremely reactive and immediately removes electrons from any molecule in its path, turning that molecule into a free radical and thus propagating a chain reaction. Actually, hydrogen peroxide is even more damaging to DNA of microbes than the hydroxyl radical, because the lower reactivity of hydrogen peroxide provides enough time for the molecule to travel into the nucleus of the cell, subsequently reacting with macromolecules such as DNA.

This discovery may find application in reducing microbial, mineral and chemical concentrations. As an example, a 3% solution of hydrogen peroxide can be expected to eliminate approximately 30% of microbes that are exposed to it. Radiation of a wavelength between 300 nanometers and 600 nanometers can be expected to eliminate 3% of the microbes exposed to it. However, when 3% hydrogen peroxide and radiation of a wavelength between 300 nanometers and 600 nanometers are administered together, the resulted synergistic reaction may eliminate 99.9999% of microbes exposed to the compound for minutes, hours and days. This is an example of the synergistic reaction and the residual effect of the generated EMODs.

Also, this discovery may find application in elimination and reduction of bacterial biofilms. In an example, a biofilm of bacteria was exposed to light of wavelengths of 300 to 600 nm for 30 to 60 seconds while in the presence of 3 to 300 mM of an oxidizing agent. Microbial counts from each treated sample were compared with those of the control samples. The results showed that the combination of the light and oxidizing agent successfully penetrated all layers of the biofilm, creating an excellent antibacterial effect. The ability of noncoherent light in combination with the oxidizing agent to affect bacteria in deep layers of biofilm illustrates that this treatment may be applied in biofilm-related microbial contamination, microbial influenced corrosion and biofilm elimination as a minimally invasive antibacterial procedure.

Combination of Oxidizing Agent Compositions and Radiation

New research demonstrates that compositions containing oxidizing agents may undergo the synergistic reaction with certain wavelengths of radiation, before the compound is applied to a target, after the compound is applied to the target or while the compound is applied to the target. This presents a tremendous advantage over current methods. Oxidizing agent compounds administered together with radiation of certain lengths to crude oil, gas, hydrocarbons, water, wastewater, production fluids, soil, air and other contaminated substances, or to surfaces in need of treatment for the effective mitigation and/or elimination of microbes, minerals, chemicals and biofilms, and particularly, microbes and biofilms in anaerobic conditions. Exemplary embodiments shown and described herein show that oxidizing agents and compounds that are functionally equivalent to oxidizing agents can form a synergistic reaction when combined with radiation of certain wavelengths. In particular embodiments, such combination of oxidizing agent compositions and radiation may significantly reduce microbial, mineral and chemical concentrations in the targeted hydrocarbon and/or reduces the formation of biofilms on liquid surfaces and on equipment, and consequently may be used to reduce, mitigate, or eliminate microbial contamination, mineral contamination, chemical contamination and/or microbial influenced corrosion on metal surfaces, in particular, metal surfaces on equipment involved in the storage, transport, and processing of the crude oil, gas, hydrocarbons, water, wastewater, production fluids, soil, air and other contaminated substances. Such equipment may be pipelines, storage tanks, cooling system (closed or open loop system), transport equipment, and refinement processing equipment.

In some embodiments, the oxidizing composition in combination with radiation may be extremely effective in reducing, eliminating, or blocking biofilm formation in anaerobic environments, which was not previously known or appreciated.

Oxidizing agents may be those synthesized by a variety of methods. Oxidizing agents and their derivatives may be obtained commercially from a wide range of sources that will be known by the skilled artisan. Oxidizing agents may also be naturally occurring. Oxidizing agents are widely distributed in the natural environment and can be produced by a variety of bacteria. For example, oxidizing agents can be produced by bacteria as a degradation product. As an intercellular signal molecule, H₂O₂ regulates various aspects of bacterial physiology. Table 1 lists common oxidizing agents and their corresponding products as non-limiting examples.

TABLE 1 Oxidizing Agents Product(s) oxygen (O₂) Various products, including the oxides H₂O and CO₂ peracetic acid Various products, including H₂O, O₂, and CO₂ ozone (O₃) Various products, including ketones, aldehydes, and H₂O; see ozonolysis fluorine (F₂) F⁻ chlorine (Cl₂) Cl⁻ bromine (Br₂) Br⁻ iodine (I₂) I⁻, I⁻ ₃ hypochlorite (ClO⁻) Cl⁻, H₂O chlorate (ClO⁻ ₃) Cl⁻, H₂O nitric acid (HNO₃) nitric oxide(NO) NO₂ nitrogen dioxide SO₂ (sulfur dioxide) sulphur (ultramarine production, commonly reducing agent) Hexavalent chromium Cr³⁺, H₂O H₂O₂, other peroxides Various products, including oxides and H₂O

The disclosed invention also contemplates the use of oxidizing agent analogs or equivalent compounds. “Oxidizing agent equivalent” or “oxidizing analog or functionally equivalent compound, molecule or derivative” or similar terms may include any known or yet unknown compounds that have a structure that is similar to oxidizing agents to a degree such that they can produce the same or similar biological effects as oxidizing agents. Such analogs or functionally equivalent compounds may be obtained in various ways, including isolation from nature, chemical modification, or via chemical synthesis.

In certain embodiments, the oxidizing agent compositions combined with radiation for use in the exemplary methods may be prepared to have any useful properties that may be appropriate or advantageous to the particular substance or surface to be treated. The exact ingredient of the oxidizing agent compositions may depend on various factors, e.g., whether the substance/surface to be treated is under aerobic or anaerobic conditions, the pH and salinity of the substance/surface to be treated, the consortium or population characteristics of the bacteria present in the biofilm of the target substance/surface to be treated, the type and composition of minerals and chemicals that may be targeted, the properties of the biofilm to be treated, among other characteristics.

The oxidizing agent compositions combined with radiation may also include components that may help stabilize and/or improve the oxidizing agents as the active ingredient, or components that may facilitate delivery of the oxidizing agents. For example, the oxidizing agent compositions herein described may also include surfactants or disruption agents and the like which may increase the permeability and/or disruption of the biofilm to facilitate the movement of the oxidizing agent composition into the biofilm and into contact with the bacteria therein.

Surfactants are well known in the art and include anionic surfactants (e.g., ammonium lauryl sulfate, sodium lauryl sulfate (SDS, sodium dodecyl sulfate, another name for the compound), sodium lauryl ether sulfate (SLES), and sodium myreth sulfate; sodium stearate, sodium lauroylsarcosinate), cationic surfactants (Octenidine dihydrochloride, Cetylpyridinium chloride (CPC), Benzalkonium chloride (BAC), Benzethonium chloride (BZT), 5-Bromo-5-nitro-1,3-dioxane, Dimethyldioctadecylammonium chloride, Cetrimonium bromide, Dioctadecyl dimethylammonium bromide (DODAB)), and nonionic surfactants (Polyoxyethylene glycol alkyl ethers, Polyoxypropylene glycol alkyl ethers, Glucoside alkyl ethers, Polyoxyethylene glycol octylphenol ethers (e.g., Triton-X), Polyoxyethylene glycol alkylphenol ethers, Glycerol alkyl esters, Polyoxyethylene glycol sorbitan alkyl esters, Polyethoxylated tallow amine (POEA)), as well as biosurfactants (surface active substances synthesized by living cells).

When administering the oxidizing agent composition in combination with radiation of certain wavelengths to a site targeted for treatment (e.g., a surface having MIC, MINC, CC or a substance having MC), the composition may be administered or delivered in an amount or dosage sufficient to provide an effective amount of the oxidizing agent composition in combination with radiation or oxidizing agent composition analog in combination with radiation. The term “effective amount of the oxidizing agent or oxidizing agent analog” is the minimal amount, level, or concentration of the oxidizing agent or oxidizing agent analog which results in a measurable or detectable effect on the substance or metal surface to be treated, in particular, on the MC, MINC, CC, MIC or the associated biofilm itself. Due to the increased EMODs generated by the method of this invention, the effective amount of the oxidizing agent will be lower than previous applicable concentrations. The effective amount can be measured in terms of concentration as parts-per-million (ppm), percentages or any suitable measurement.

In certain embodiments, the effective amount of the oxidizing-agent-containing compositions provides a concentration of the oxidizing agent compound that is between about 0.001 percent to 100 percent or more of the volume of the hydrocarbon or other substance to be treated, such as between about 0.001 percent and about 1 percent, or between about 0.001 and about 50 percent. However, it will be clear to a person skilled in the art that this term may refer to any suitable concentration that is necessary to achieve the desired effects.

Although any treatment methods similar or equivalent to those described herein can also be used in the practice or testing of the present disclosure, some exemplary methods are now described.

Treatment Methods and Applications

As shown in the exemplary embodiments, the combination of oxidizing agents and radiation of certain wavelengths may form a synergistic reaction. The synergistic reaction may generate EMODs, which may be effective in reducing microbial count, mineral contamination, chemical contamination and eliminating or blocking biofilm formation, particularly in anaerobic environments. Prior to the invention described in this disclosure, this synergistic reaction involving oxidizing agents and radiation of certain wavelengths was not known or appreciated as to its relationship to EMOD creation and EMOD longevity or its effect on microbial contamination (MC), mineral contamination (MINC), chemical concentration (CC), microbial influenced corrosion (MIC) or biofilm creation. MC, MINC, CC, MIC and biofilm may be eliminated or greatly reduced with the disclosed treatment methods in or on equipment including pipelines, storage tanks, transport and refinery processing equipment.

In one aspect, the embodiment may relate to a method for reducing microbial concentration, mineral contamination, chemical contamination or for reducing biofilm formation to mitigate or eliminate microbial contamination, mineral contamination, chemical contamination and/or microbial influenced corrosion on a metal surface. The method may include contacting the substance or metal surface to be treated with an effective amount of a composition comprising an oxidizing agent or a functionally equivalent analog or derivative thereof, and exposing the resulted mixture of the substance or metal surface to be treated and the composition to radiation of certain wavelengths. The radiation may be applied to the oxidizing agent before it is applied to the target, while it is applied to the target or after it is applied to the target. This aspect of the invention has not been previously reported in literature. The ability to greatly increase the performance of an oxidizing agent before it is applied to a target creates new application modalities. The oxidizing agent and the radiation together form a synergistic reaction, resulting in an antimicrobial effect that is stronger than the sum of that of the oxidizing-agent-based composition and radiation when acting separately. The synergistic reaction also creates EMODs that exist for seconds, minutes, hours and days. The discovery of the existence of EMODs that last for longer than a few nanoseconds is a new and previously unreported, undiscovered, property of the technology described in this patent application. In other aspects, the disclosure may relate to corresponding combination and device for reducing microbial concentration, mineral contamination, and chemical concentration or for reducing biofilm formation to mitigate or eliminate microbial contamination, mineral concentration, chemical concentrations and/or microbial influenced corrosion on a metal surface.

The method disclosed herein may also include additional upstream and/or downstream testing steps that facilitate knowing whether and how to administer the treatment involving an oxidizing agent composition combined with radiation of certain wavelengths. Such additional steps may aim to determine whether a target system has a legitimate MC, MINC, CC and/or MIC risk at a particular site (e.g., a crude pipeline that transports crude oil from an offshore rig to a distant domestic refinery). Other steps may also involve subsequent monitoring steps to evaluate the extent of the MC, MINC, CC and MIC associated biofilm, followed then by steps to carry out a particular treatment plan of the oxidizing agent composition compound combined with radiation of certain wavelengths, e.g., an aggressive treatment plan or a lower strength treatment plan.

For example, corrosive damage to a pipeline may be detected as a result of regularly scheduled maintenance along a certain ten-mile stretch of crude oil pipeline. In order to learn more about the extent and nature of the damage, and therefore to determine an appropriate treatment, a user may sample the environmental conditions at various points along the pipeline by assessing properties that would be indicative of conditions suitable for biofilm formation, including, but not limited to: (a) detection of certain bacterial species known to have a role in bacterial corrosion (e.g., sulfate reducing bacteria), (b) detection of certain corrosive metabolites (e.g., presence of organic acids, hydrogen sulfide gas, or the like), (c) existence of suitable pH and temperature conditions known to be supportive of biofilm development, (d) presence of an aqueous environment (e.g., extent of water dropout or separation of a water phase from the crude oil), (e) slow flow rate (which is known to be conducive to biofilm formation), and (f) existence of high bacterial biomass. The person of ordinary skill may also wish to examine physical samples collected from the pipeline wall to detect and characterize the biofilm (e.g., thickness) or metal coupon samples placed into the flow path. Such factors may be evaluated and then assessed by the skilled person to design a specifically tailored oxidizing agent compound combined with radiation of certain wavelengths, resulting in a synergistic-reaction-based treatment. This synergistic reaction creates EMODs that exist for longer periods of time then has previously ever been recorded. This characteristic of this disclosure allows treatments of these issues with lower levels of oxidizing agents and it allows for a treatment that lasts for a greater period of time when compared to a similar dose of an oxidizing agent from methods that were in use previously to this disclosure.

In some embodiments, variables affecting the specific nature of any given synergistic-reaction-based treatment involving oxidizing agent compounds combined with radiation of certain wavelengths may include, for example: (a) pH of the oxidizing agent compound composition, (b) salinity of the oxidizing agent compound composition, (c) concentration of the oxidizing agent compound in the composition (e.g., 1%, 2%, 5%, 10%, 50%, w/v), (d) target or desired concentration of the oxidizing agent compound composition once delivered in the flow path (e.g., 1 ppm, 2 ppm, 4 ppm, 10 ppm, 50 ppm, 100 ppm, 500 ppm, 1000 ppm or more), (e) the rate of flow of the substance to be treated, (f) the rate of injection of the oxidizing agent compound composition, (g) the types of bacteria present in the consortium of the biofilm, (h) the level of bacterial biomass and/or biofilm present, (i) the presence of visible evidence of corrosion (e.g., pits) (which generally is associated with the degree of corrosion in an increasing linear relationship), and (j) the detection of metal loss on test coupons. Each of these factors may be assessed, along with other available factors, to gauge the severity of the MC, MINC, CC and MIC risk and/or the degree of biofilm-associated corrosion. Once the severity of the corrosion is known, the skilled person can determine the best course for administering the treatment (i.e., the oxidizing agent compound composition combined with radiation of certain wavelengths).

Treatment may be aggressive in nature, or otherwise less aggressive, depending on the degree and severity of the MC, MINC, CC and/or MIC and/or biofilm formation. For example, if the degree of biofilm associated corrosion is determined to be low, a gentle treatment may be administered by, for example, reducing the total amount or concentration of the oxidizing agent compound composition combined with radiation of certain wavelengths delivered, reducing the number of hours of continued injection into the site of interest, or increasing the number of days spanning between follow-up injections. However, if the degree of biofilm associated corrosion is determined to be high, a more aggressive treatment may be administered by, for example, increasing the total amount or concentration of the oxidizing agent compound combined with radiation of certain wavelengths delivered, increasing the time period for continuous injection, or shortening the number of time or days between successive treatments.

The oxidizing-agent-based compositions combined with radiation of certain wavelengths of the disclosure may be used to treat any affected surface, and in particular, any affected metal surface on any equipment involved in the storage, transport, and/or processing of the substance to be treated. For example, affected surfaces may include a pipeline that transports crude oil from onshore or offshore drill site or from hydraulic fracturing sites to local or distant petroleum and/or natural gas refineries. Problematic biofilms may form along the interior surfaces of wastewater pipelines over distances that extend over many miles or tens of miles, leading to corrosive conditions over a multitude of points. It is generally accepted that pipeline corrosion represents the majority of corrosive damage due to MC, MINC, CC and MIC in transport of the substance, particularly given that there are over 190,000 miles of liquid pipelines in the US alone. In another example, affected surfaces may include storage facilities at refinery sites or those located on transport tankers. Other equipment, such as pumps, valves, and other equipment that comes into contact with the flow path of the substance, is susceptible to the formation of biofilms and thus to MC, MINC, CC and MIC. Any and all of these sites and surfaces may be treated using the methods disclosed herein.

Exemplary FIG. 1 depicts a diagram showing an embodiment in which the method is applied in a storage tank of crude oil, gas, hydrocarbons, water, wastewater, production fluids, soil, air or other contaminated substance. As illustrated in FIG. 1, water 10 is accumulated on the bottom of the tank during storage of the substance 20. The substance 20 has a density or specific gravity less than that of water, and thus floats on the surface of water 10. Typically, bacteria and/or fungi that invade the tank thrive at the interface between the substance layer and the water layer, obtaining water from water 10 while obtaining carbon as “food” from the substance 20. Also, the greatest microbial contamination (MC) normally occurs at the substance-water interface because the bacterial life is well supported there. Moreover, at the locations 50 where the substance-water interface touches the metal tank, the greatest microbial influenced corrosion (MIC) may be observed. The rapid growth of the microorganisms such as fungi, bacteria, yeast at the substance-water interface not only leads to formation of corrosive biofilms, their metabolic products may further form larger agglomerates, causing precipitation of sludge 30 on the bottom of the tank. Microbial influenced corrosion (MIC) may be observed at the locations where sludge 30 touches the metal tank as well.

In the method according to this exemplary embodiment, an effective amount of the composition comprising the oxidizing agent compound, or a functionally equivalent analog or derivative thereof may be administered into the substance to be treated. In certain embodiments, the effective amount of composition may be administered into the water that exists in the tank. Because the microbes require water to survive and multiply, treating the water with the oxidizing agent while exposing the mixture to certain wavelengths of radiation creates EMODs that reduce or eliminate the MC, MINC, CC MIC and/or biofilm. In some embodiments, the composition comprising the oxidizing agent compound may be introduced into the tank via a pump or other automated means. In other embodiments, the oxidizing-agent-based composition may be introduced manually.

A radiation emission mat 41 may be arranged inside the storage tank, near to the target areas to be treated. A typical target area may be the interface between water and the substance to be treated. With its density or specific gravity properly calibrated, the radiation emission mat 41 can be kept in the storage tank at a desired location, e.g., floating at the substance-water interface, suspended from an anchor element above the storage tank or above the desired location of disposal of mat 41, supported and held in place by an anchor element at or near a bottom portion of a storage tank, or otherwise fixed in place in the storage tank through any fixing elements, as desired. The radiation emission mat 41 may emit radiation of certain wavelengths, e.g., a wavelength between 300 nm and 600 nm. In certain embodiments, the radiation emission mat 41 is movable so that it may be controlled to stay at a desired location relative to the target areas. The wavelength, intensity and/or time of duration of the radiation emitted from the mat 41 also may be adjustable, for example a wavelength between 300 nm and 600 nm.

FIG. 2 depicts a diagram showing another exemplary embodiment in which the method is applied in a storage tank of crude oil, gas, hydrocarbons, water, wastewater, production fluids, soil, air or other contaminated substance. As illustrated in FIG. 2, the substance 20 has a density or specific gravity greater than that of water, and thus water 10 that is accumulated in the storage tank is floating on the surface of the substance 20. Similarly, the greatest microbial contamination (MC) may be observed at the substance-water interface, and the greatest microbial influenced corrosion (MIC) at the locations 50 where the substance-water interface touches the metal tank. Microbial influenced corrosion (MIC) may be observed at the locations where sludge 30 touches the metal tank as well.

Oxidizing agent compounds may be similarly introduced into the storage tank manually, by a titration system 38, or via a pump 40. At least one radiation emission mat may be arranged inside the tank, near to the target areas to be treated. The target areas may include, but are not limited to, the substance-water interface and the bottom of the storage tank. In certain embodiments, with their density or specific gravity properly designed, a radiation emission mat 41 may be arranged floating at the substance-water interface, while a second radiation emitting mat 42 may be provided as resting on the bottom of the storage tank, near to sludge 30. The radiation emission mats 41 and 42 may emit radiation of certain wavelengths, for example a wavelength between 300 nm and 600 nm.

Exemplary FIG. 3 depicts a diagram showing an embodiment in which the method is applied in a length of transport pipeline. The present embodiment may be used in a length of pipeline of crude oil, gas, hydrocarbons, water, wastewater, production fluids, air or other contaminated substances. In this embodiment, a band 70 with radiation producing function may be arranged inside the pipeline 60, in the form of a lining layer on the wall of the pipeline 60. An effective amount of a composition comprising an oxidizing agent compound, or a functionally equivalent analog or derivative thereof may be administered into the pipeline 60. The radiation producing band 70 may emit radiation of certain wavelengths, for example a wavelength between 300 nm and 600 nm.

Referring now to exemplary FIG. 4, in this embodiment treatment can be provided in various stages. Here, the substance to be treated 80 flows, is pumped, or is otherwise put into tank 81, which could also be a pipe, pipeline, storage container, or the like. Tank 81 is such that substance to be treated 80 is mixed or interspersed with an oxidizing agent 87, as described throughout the exemplary embodiments. The oxidized substance to be treated 80 then flows through conduit 82 into tank 83. In tank 83, the oxidized substance to be treated 80 is exposed to radiation 86 to cause the synergistic reaction. Treated substance 85 then flow out through conduit 84 to a desired location. For example, treated substance 85 could flow to another storage tank that is commutatively coupled to tank 81. Alternatively, treated substance 85 could be transported via a further pipe or pipeline to another location.

The method can further be implemented in the form of a closed loop or open loop system so as to decontaminate the substance in a storage tank, transport device, pipeline or other area where contamination may occur. Exemplary FIG. 5 depicts a diagram showing an embodiment in which the method is applied in the form of a closed loop system for decontaminating a substance to be treated, whereas exemplary FIG. 6 depicts a diagram showing exemplary an embodiment in which the method is applied in the form of an open loop system for decontaminating a substance to be treated. An oxidizing agent is added to the contaminated substance and the oxidizing agent is exposed to certain wavelengths of radiation before it's added to the contaminated substance or while it's added to the contaminated substance or after it is added to the contaminated substance. Exemplary FIG. 7 depicts a diagram showing an embodiment in which the method is applied in the form of an oxidizing agent compound that is exposed to radiation of a certain wavelength in a reservoir before the oxidizing agent compound is administered to the target substance to be treated This oxidizing agent compound may be irradiated to initiate the synergistic reaction before the oxidizing agent compound is applied to the target, while the oxidizing agent is applied to the target, after the oxidizing agent is applied to the target or a combination of these methods. The synergistic reaction creates EMODs that destroy microbes and precipitates contaminates. These EMODs exist for a previously undiscovered time consisting of seconds, minutes, hours and days. This is in contrast to the previously recorded time life of EMODs that was a few nanoseconds.

The system depicted in FIG. 5 is, for example, suitable for decontamination of a substance in a reaction container 33. The system is provided with a float 22, which has a specifically designed structure and specific gravity that allows it to rest in a layer where microbes and/or contaminants are concentrated, e.g., the interface of oil and water. A circulating pump 11 equipped with sensors injects a desired amount of oxidizing agent compound into the reaction container 33. This injected oxidizing agent compound may have been exposed to radiation creating the EMOD generating synergistic reaction before it was applied to the target, while it was applied to the target, after it was applied to the target or a combination of the three. After the synergistic reaction takes place, the oil is returned to its storage container, for example, oil tanks. Although FIG. 5 shows an instance in which the system is applied for decontamination of oil, it will be understood that this system can be used to decontaminate various other contaminated substances as needed.

The system depicted in FIG. 6 is, for example, suitable for decontamination of a substance flowing in a pipeline 33. In this exemplary embodiment, an oxidizing agent injector 11 equipped with sensors is arranged in the upstream of a radiation emitting device 22. This injected oxidizing agent compound may have been exposed to radiation creating the EMOD generating synergistic reaction before it was applied to the target, while it was applied to the target, after it was applied to the target or a combination of the three. After the synergistic reaction takes place, the treated substance continues flowing further downstream for its intended use or further storage.

In certain embodiments, various sensors may be provided to detect variables including, but not limited to pH, temperature, density, oxygen concentration of the substance stored in the tank or transported through the pipeline. Further, the effective amount of the composition comprising the oxidizing agent compound, or a functionally equivalent analog or derivative thereof may be determined on the basis of any one or more of the density and light absorbing quality of the substance to be treated, and the size and shape of the container (tank, pipeline, or the like) thereof.

In certain embodiments, the formulation of the oxidizing agent composition may be determined on the basis of whether the substance to be treated is under aerobic or anaerobic conditions, pH of the substance, salinity of the substance, consortium or population characteristics of the microorganism present in the substance, the microbial content of the substance and/or the microbial content of the biofilms.

In certain embodiments, the wavelength, intensity, duration time and/or location relative to the substance to be treated, of the radiation, may be determined on the basis of any one or more of the density and light absorbing quality of the substance, the size and shape of the container thereof, whether the substance is under aerobic or anaerobic conditions, pH of the substance, salinity of the substance, consortium or population characteristics of the microorganism present in the substance, and the microbial content of the biofilms.

In certain embodiments, the person of ordinary skill in the art will easily be able to assess the degree of biofilm associated corrosion or contamination based on various measurable inputs and accordingly determine a proper course of the oxidizing agent compound combined with a radiation of certain wavelengths without undue experimentation.

Combination Treatments

Exemplary embodiments shown and described herein relate, in part, to the discovery that oxidizing agents or compounds that are functionally equivalent may form a synergistic reaction together with radiation of certain wavelengths. The resulting synergistic reaction may result in a product that may significantly reduce the formation of microbes, mineral contamination, chemical contamination and biofilms in the substance to be treated and on surfaces, and consequently, may be used to reduce, mitigate, or eliminate microbial contamination, mineral contamination, and/or chemical contamination associated with the substance to be treated and/or microbial influenced corrosion on metal surfaces, in particular, metal surfaces on equipment involved in the storage, transport, and processing of the substance to be treated. In particular embodiments, the product of the synergistic reaction involving the oxidizing agents and radiation, EMODs, may be effective in reducing, eliminating, or blocking microbes and biofilm formation in anaerobic environments, which prior to the disclosure was not known or appreciated. Such equipment can include pipeline, storage tanks, supply systems and processing equipment.

The synergistic reaction associated with oxidizing agents and radiation methodologies herein disclosed may be advantageous over existing mitigation practices at least because: (a) the oxidizing agents may be a natural product of environmental bacteria, hence minimal environmental impact compared to currently available biocides; (b) current biocides are naturally taken up by bacteria in a biofilm and induce a switch to planktonic growth behavior (i.e., growth away from biofilm environment) and thus, lack biofilm permeability aspects needed to better eliminate MC, MINC, CC and MIC; (c) this MC, MINC, CC and MIC eliminating or reducing treatment may be compatible with commercial corrosion inhibitors, whereas many current biocides are not; (d) Further, the synergistic reaction between the oxidizing agents and the radiation presents no negative environmental impact, which is unique compared with current methods of treating MC, MINC, CC and MIC, and thus this invention results in a more complete elimination or reduction in MC, MINC, CC and MIC than currently available methods; and (e) the reduction in MC, MINC, CC and MIC is significantly greater than currently available methods.

Moreover, the disclosed synergistic reaction treatment methods involving oxidizing agent compound combined with radiation of certain wavelengths may be also contemplated to be combined with other MC, MINC, CC and/or MIC mitigation strategies, such as the use of corrosion resistant metals, temperature control, pH control, radiation, filtration, protective coatings with corrosion inhibitors or other chemical controls (e.g., biocides, oxidizers, acids, alkalis), bacteriological controls (e.g., phages, enzymes, parasitic bacteria, antibodies, competitive microflora), pigging (i.e., mechanical delamination of corrosion products), sonication, stirring (the introduction of movement in the substance to be treated), anodic and cathodic protection, and modulation of nutrient levels.

For instance, in certain embodiments relating to pipeline treatment, the pipeline may be first treated with pigging. The pigging can help not only to physically remove the biofilm, but also acts to disturb the biofilm such that the permeation of the biofilm is improved, thereby rendering the synergistic reaction treatment involving oxidizing agent compounds combined with radiation of certain wavelengths more effective. Methods and equipment for pigging pipelines are well known in the art and thus are not described in detail here.

EXAMPLES

This disclosure may be further demonstrated by the following examples which should not be construed as limiting. The contents of all references, including any publicly available polypeptide and/or nucleic acid sequences accession numbers (e.g., GenBank), and published patents and patent applications cited throughout the application are hereby incorporated by reference. Persons of ordinary skill in the art will recognize that the disclosure may be practiced with variations on the disclosed structures, materials, compositions and methods, and such variations are regarded as within the ambit of the disclosure.

Example 1

Example 1 may demonstrate reduction of MC, MINC, CC and MIC associated with Desulfoviberio vulgaris Hildenborough (DvH) growing on carbon steel in the presence of oxidizing agent compounds combined with radiation of certain wavelengths which may result in a synergistic reaction.

In Example 1, carbon steel coupons were incubated in the presence of oxygen and, as the oxidizing agent compound, hydrogen peroxide, combined with radiation of certain wavelengths of 300 nm to 500 nm in a synergistic reaction, with and without an inoculum of DvH. The metal loss of the carbon steel coupons was measured. The results show that coupons incubated with DvH experienced approximately a 2-fold more weight loss than those incubated in a sterile environment. Additionally, the data shows that oxidizing agent compounds combined with radiation of certain wavelengths of 300 nm to 500 nm in a synergistic reaction creates EMODs that reduce and/or eliminate corrosion in the presence of DvH (MIC) compared to the no oxidizing agent compound combined with radiation of certain wavelengths of 300 nm to 500 nm in a synergistic reaction treatment, and that this reduction in weight loss is not replicated in a sterile environment without DvH inoculation. Therefore, the experiment demonstrates that oxidizing agent compounds combined with radiation of certain wavelengths in a synergistic reaction has inhibitory effect on corrosion is MIC specific.

Example 2

Example 2 may demonstrate that microbial contamination MC, mineral contamination (MINC), chemical contamination (CC) and Microbial Induced Corrosion (MIC) by DvH is reduced by different concentrations 100 ppm, or 0.01%, of the oxidizing agent compound hydrogen peroxide combined with radiation of certain wavelengths at 300-500 nm in a synergistic reaction.

In example 2, steel coupons were incubated in cultures of DvH for three days with and without exposure to an oxidizing agent compound, specifically hydrogen peroxide, combined with radiation of certain wavelengths 300-500 nm in a synergistic reaction and then the coupons were measured to determine the amount of metal loss due to corrosion. Coupons incubated in the absence of an oxidizing agent compound combined with radiation of certain wavelengths in a synergistic reaction resulted in nearly 2-fold more metal loss than the coupons grown in the presence of an oxidizing agent compound combined with radiation of certain wavelengths in a synergistic reaction. The data demonstrates that the metal coupons in the presence of the oxidizing agent compound combined with radiation of certain wavelengths in a synergistic reaction displayed little to no corrosion. Therefore, the experiment demonstrates that oxidizing agent compounds combined with radiation of certain wavelengths in a synergistic reaction inhibit corrosion of metal caused by anaerobic biofilms formed from sulfate-reducing bacteria.

Example 3

Example 3 may demonstrate the treatment of a pipeline with an oxidizing agent compound, hydrogen peroxide, combined with radiation of certain wavelengths 300-500 nm in a synergistic reaction to inhibit microbial influenced corrosion, mineral contamination, chemical contamination and associated biofilm formation

In example 3, steel pipelines are used to transport seawater from treatment and pumping facilities to oil field water injection wells. The water is injected into specific regions of an oil-producing reservoir to provide secondary oil recovery. This provides additional oil recovery over that which results from primary, or natural, production due to the initial pressurization of the reservoir.

Treatment of the seawater prior to entering the pipeline is required to prevent corrosion of the steel pipeline and the steel tubing in the water injection wells and to improve injected water quality. The treatment process may include chlorination, filtration, deaeration, and addition of a solution of an oxidizing agent compound combined with radiation of certain wavelengths in a synergistic reaction. The chlorination kills the majority of the bacteria and algae entering the system with the water from the sea. The filtration removes most of the sea sediments, large particles, and biomass. Deaeration of the water is critical to remove oxygen, a key element involved in the corrosion process. Deaeration of the seawater to less than about 20 ppb oxygen essentially eliminates the potential for common oxygen-induced corrosion. Unfortunately, removing the oxygen results in an anaerobic environment, which increases the potential for anaerobic corrosion of the steel pipeline due to the activity of sulfate-reducing bacteria in the system and other categories of bacteria. Addition of a solution of an oxidizing agent (or functionally equivalent analog thereof), such as hydrogen peroxide, combined with radiation of certain wavelengths, such as 300-500 nm, in a synergistic reaction will be introduced to control the activity of the corrosion inducing sulfate-reducing bacteria and other biofilm-forming bacteria that lead to corrosion, such as iron-oxidizing bacteria, sulfur-oxidizing bacteria, nitrate reducing bacteria, methanogens, and acid producing bacteria, among others. Also, the addition of a solution of an oxidizing agent (or functionally equivalent analog thereof) combined with radiation of certain wavelengths in a synergistic reaction will be introduced to removed unwanted concentrations of mineral and chemicals.

Example 4

Example 4 may demonstrate that MC by anaerobic bacteria Staphylococcus epidermidis ATCC 12228 with or without the presences of MNC, by iron, is reduced by either 3% or 0.3% hydrogen peroxide as the oxidizing agent compound combined with radiation of certain wavelengths at 400 nm to 420 nm, thereby providing a synergistic reaction. Moreover, the results demonstrate that the oxidizing agent compound can be exposed to radiation prior to contact with the target and exposed to radiation a second time to reactivate of the antimicrobial effect.

Specifically, solutions of 3% hydrogen peroxide, 0.3% hydrogen peroxide, 3% hydrogen peroxide with iron (20 mL of 3% H₂O₂ with 0.5 mL of 0.1N FeSO₄) and 0.3% hydrogen peroxide with iron (2 mL of 3% H₂O₂ with 18 mL of Sterile DI Water and 0.5 mL of 0.1N FeSO₄) were tested. Each test substance was treated with light of 400 to 420 nm for 1 minute, then applied to a target (a carrier with a viable bacteria concentration of approximately 1×10⁶ cells or greater). The solutions were applied to the targets after the dwell times of 1 minute, 5 minutes, 10 minutes, 30 minutes, 1 hour, 12 hours, 24 hours, 2, days, 5 days, and 7 days. After 7 days of dwell time, all solutions were treated with light again for 1 minute, and a target was treated after 1 minute of dwell time. The results are summarized in Table 1.

TABLE 1 Time after solution 3% H₂O₂ 0.3% H₂O₂ 3% H₂O₂ with iron 0.3% H₂O₂ with iron exposed % % % % Control to light CFU Reduction CFU Reduction CFU Reduction CFU Reduction CFU per prior to per vs. per vs. per vs. per vs. Time carrier application carrier Control carrier Control carrier Control carrier Control 0 6.04E+05 0 N/A N/A N/A N/A N/A N/A N/A N/A 1 min 7.00E+04 88.42% 1.10E+04 98.18% 3.80E+04 93.71% 1.41E+05 76.67% 5 min 7.00E+04 88.42% 3.00E+04 95.04% 4.00E+04 93.38% 5.38E+04 91.10% 10 min 3.10E+04 94.87% 1.98E+05 67.24% 8.50E+04 85.93% 2.13E+04 64.75% 30 min 2.80E+04 95.37% 7.00E+04 88.42% 7.10E+04 88.25% 6.88E+04 88.62% 1 hr 7.10E+04 88.25% 7.00E+04 88.42% 7.00E+04 88.42% 9.10E+04 84.94% 12 hr 9.20E+04 12 hr 1.80E+04 80.43% 1.27E+05 nr 8.10E+04 11.96% 1.10E+05 nr 24 hr 1.33E+05 24 hr 2.10E+04 84.21% 1.40E+04 89.47% 1.60E+04 87.97% 1.55E+05 nr 2 days 3.00E+05 2 days 9.00E+04 70.00% 2.64E+05 12.00% 8.70E+04 71.00% 3.39E+05 nr 5 days 4.50E+04 5 days 3.29E+03 92.69% 4.40E+04 2.22% 1.60E+04 64.44% 2.43E+03 94.60% 7 days 9.80E+04 7 days 1.50E+04 84.69% 7.70E+04 21.43% 2.07E+05 nr 7.10E+04 27.55% 7 days* 1.00E+04 89.80% 1.03E+05 nr 3.00E+04 69.39% 2.30E+04 76.53% *= reactivation with light of 400 to 420 nm for 1 minute; nr = no reduction

EQUIVALENTS

The foregoing description and accompanying figures illustrate the principles, exemplary embodiments, and modes of operation of the invention. However, the invention should not be construed as being limited to the particular exemplary embodiments discussed above. Additional variations of the exemplary embodiments discussed above will be appreciated by those skilled in the art. Using no more than routine experimentation, one skilled in the art will recognize or be able to ascertain, many equivalents to the specific embodiments and methods described herein. Such equivalents are intended to be encompassed by the scope of the following claims.

Therefore, the above-described exemplary embodiments should be regarded as illustrative rather than restrictive. Accordingly, it should be appreciated that variations to those exemplary embodiments can be made by those skilled in the art without departing from the scope of the invention as defined by the following claims. For example, the relative quantities of the ingredients may be varied to optimize the desired effects, additional ingredients may be added, and/or similar ingredients may be substituted for one or more of the ingredients described. Additional advantageous features and functionalities associated with the methods, combinations and devices of the present disclosure will be apparent from the appended claims. 

What is claimed is:
 1. A system for reducing microbial, and/or mineral, and/or chemical concentration in a substance, and/or for reducing biofilms formed in the substance, on the surface of the substance, or on the surface of equipment involved in the storage, transport or processing of the substance, comprising: an oxidizing agent introducing device for introducing an effective amount of a composition comprising an oxidizing agent compound into the substance to be treated; and at least one radiation emitting device for exposing the composition comprising the oxidizing agent compound to radiation of certain wavelengths for periods of time ranging from less than 1 second to days, wherein the radiation emitted by the at least one radiation emitting device is selected from the group consisting of particle radiation, acoustic radiation, and electromagnetic radiation selected from the group consisting of ultraviolet light, visible light, x-rays, and gamma (γ) radiation, wherein the system is adapted for use in a pipeline in which the substance to be treated flows, and the at least one radiation emitting device is a lining layer for inside a pipeline for transporting the substance to be treated, and the oxidizing agent compound introducing device is positioned at a location along the pipeline to administer the composition comprising an oxidizing agent compound into the pipeline.
 2. The system of claim 1, wherein the substance to be treated is crude oil, gas, hydrocarbons, water, wastewater, frack water, food, produce, animals, production fluids, soil, or air.
 3. The system of claim 1, wherein the oxidizing agent compound introducing device is positioned at one of: a location, relative to a direction that the substance flows in the pipeline, that is upstream of the at least one radiation emitting device so that the oxidizing agent compound is exposed to radiation emitted from the at least one radiation emitting device after being introduced into the pipeline, a location at which the oxidizing agent is dispensed into the substance while the oxidizing agent compound is being exposed to the radiation emitted from the at least one radiation emitting device, or a location at which the oxidizing agent compound is exposed to radiation emitted from the at least one radiation emitting device before the oxidizing agent compound is introduced to the pipeline, and wherein the system is configured so that after the location in the pipeline in which the oxidizing agent compound is exposed to radiation, the treated substance continues flowing further downstream in the pipeline.
 4. The system of claim 1, wherein the system is adapted to expose the oxidizing agent compound to a radiation of a certain wavelength from the at least one radiation emitting device to create a synergistic reaction while the oxidizing agent introducing device introduces the oxidizing agent compound to the substance.
 5. The system of claim 1, wherein the system is adapted to expose the oxidizing agent compound to a radiation of a certain wavelength from the at least one radiation emitting device to create a synergistic reaction after the oxidizing agent introducing device introduces the oxidizing agent compound to a substance.
 6. The system of claim 1, wherein the radiation emitting device is configured to emit radiation of certain wavelengths between 200 nanometers and 600 nanometers.
 7. The system of claim 1, wherein the effective amount of the composition provides a minimal amount of the oxidizing agent compound to result in a measurable or detectable effect on the microbial concentration, mineral concentration, chemical concentration and/ or the biofilm formation.
 8. The system of claim 1, wherein the effective amount of the composition provides a concentration of the oxidizing agent compound that is between 0.001 percent to 100 or greater percent of the volume of the substance to be treated.
 9. The system of claim 1, wherein the effective amount of the composition comprising the oxidizing agent compound is determined on the basis of any one or more of the density, pH, temperature, viscosity and light absorbing quality of the substance to be treated, and size and shape of a container thereof.
 10. The system of claim 1, wherein the oxidizing agent compound is hydrogen peroxide, carbamide peroxide, peracetic acid, hypochlorous acid, chlorine-, or benzoyl peroxide.
 11. The system of claim 1, wherein the at least one radiation emitting device is configured to apply the radiation of certain wavelengths to the oxidizing agent more than once.
 12. A system for reducing microbial, and/or mineral, and/or chemical concentration in a substance, and/or for reducing biofilms formed in the substance, on the surface of the substance, or on the surface of equipment involved in the storage, transport or processing of the substance, comprising: an oxidizing agent introducing device for introducing an effective amount of a composition comprising an oxidizing agent compound into the substance to be treated; and at least one radiation emitter for exposing the composition comprising the oxidizing agent compound to radiation of certain wavelengths for periods of time ranging from less than 1 second to days, wherein the radiation emitted by the at least one radiation emitter is selected from the group consisting of particle radiation, acoustic radiation, and electromagnetic radiation selected from the group consisting of ultraviolet light, visible light, x-rays, and gamma (γ) radiation, wherein the system is adapted for use in a reaction container for processing the substance to be treated, and the at least one radiation emitter is a float which has a specific gravity for allowing the float to rest in a reaction container for processing the substance to be treated at a location where microbes, minerals, and chemicals are concentrated.
 13. The system of claim 12, wherein the substance to be treated is crude oil, gas, hydrocarbons, water, wastewater, frack water, food, produce, animals, production fluids, soil, or air.
 14. The system of claim 12, wherein the oxidizing agent compound introducing device is a pump for introducing the oxidizing agent into the reaction container.
 15. The system of claim 12, wherein the system is adapted to expose the oxidizing agent compound to a radiation of a certain wavelength from the at least one radiation emitter to create a synergistic reaction while the oxidizing agent introducing device introduces the oxidizing agent compound to the substance.
 16. The system of claim 12, wherein the system is adapted to expose the oxidizing agent compound to a radiation of a certain wavelength from the at least one radiation emitter to create a synergistic reaction after the oxidizing agent introducing device introduces the oxidizing agent compound to a substance.
 17. The system of claim 12, wherein the radiation emitter is configured to emit radiation of certain wavelengths between 200 nanometers and 600 nanometers.
 18. The system of claim 12, wherein the effective amount of the composition provides a minimal amount of the oxidizing agent compound to result in a measurable or detectable effect on the microbial concentration, mineral concentration, chemical concentration and/ or the biofilm formation.
 19. The system of claim 12, wherein the effective amount of the composition provides a concentration of the oxidizing agent compound that is between 0.001 percent to 100 or greater percent of the volume of the substance to be treated.
 20. The system of claim 12, wherein the effective amount of the composition comprising the oxidizing agent compound is determined on the basis of any one or more of the density, pH, temperature, viscosity and light absorbing quality of the substance to be treated, and size and shape of a container thereof.
 21. The system of claim 12, wherein the oxidizing agent compound is hydrogen peroxide, carbamide peroxide, peracetic acid, hypochlorous acid, chlorine, or benzoyl peroxide.
 22. The system of claim 12, wherein the at least one radiation emitter is configured to apply the radiation of certain wavelengths to the oxidizing agent more than once. 